TW201035690A - Acid-sensitive, developer-soluble bottom anti-reflective coatings - Google Patents

Abstract

Acid-sensitive, developer-soluble bottom anti-reflective coating compositions are provided, along with methods of using such compositions and microelectronic structures formed thereof. The compositions preferably comprise a crosslinkable polymer dissolved or dispersed in a solvent system. The polymer preferably comprises recurring monomeric units having adamantyl groups. The compositions also preferably comprise a crosslinker, such as a vinyl ether crosslinking agent, dispersed or dissolved in the solvent system with the polymer. In some embodiments, the composition can also comprise a photoacid generator (PAG) and/or a quencher. The bottom anti-reflective coating compositions are thermally crosslinkable, but can be decrosslinked in the presence of an acid to be rendered developer soluble.

Description

201035690 VI. INSTRUCTIONS: Cross-reference to related applications This application claims the priority rights of ANTI-REFLECTIVE COATINGS WITH ACID-CLEAVABLE, ADAMANTYL MONOMER IN BINDER POLYMER (Serial No. 61/153, 909) filed on February 19, 2009. The literature is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel wettable developing bottom anti-reflective coating formed using an adamantyl monomer in a polymer and having excellent reflectance control and excellent photoresist compatibility. [Prior Art] As the integrated circuit (1C) industry continues to move toward smaller feature sizes to increase information storage capabilities, outstanding anti-reflective techniques are needed to provide the critical dimension (CD) control required for 193 nm lithography. The bottom anti-reflective coating will be an anti-reflective material for critical and even non-critical applications such as implantation. The use of dyed resists under top anti-reflective coatings is not sufficient for 45 nm, 32 nm, and 22 nm node implant layers. The CD required to implant a 45 nm node is about 150 nm, and the CD required to implant a 32 nm node and a 22 nm node is about 130 nm. Although the bottom anti-reflective coating used in most modern applications is plasma. Developed type 201035690 (dry)' but the lesser use of the six layers also provides some advantages, scoop * (wet) bottom anti-reflective coating rRTF. ^ 匕 4 remove the active ions necessary for dry development in two steps φ 胄And potential damage to the plasma sensitive layer in the stack. The use of a photoresist developer in the second (four) (such as gas oxidized tetrazolium (TMAH) in addition to the exposed anti-reagent and developer soluble bottom anti-reflective spread reflective coating due to the bottom anti-reflective coating n" The removal of unexposed anti-_ is minimized: engraved budget. However, 'developer soluble bottom= can be achieved with a dry bottom anti-reflective coating to achieve resolution and typical 9 resolution is less stringent non-critical Applications, such as implant layers. A variety of positive bottom anti-reflective coating chemical platforms for the preparation of light-sensitive developers have been previously described. These bottom anti-reflective coatings are thermoset and include: a) the use of polymeric binders a dye-filled bottom P anti-reflective coating, b) a coating formed using an acid-reducing chromophore having a linking polymer = a hyperbranched polymer; or a linear polyfluorene & Coating. For these three emphasized methods, the polymer film becomes solvent insoluble (crosslinked) during the hot plate baking step. After exposure to a suitable light source and (4) exposed material (PEB), Degraded into developer soluble or water soluble However, there is still a need for a bottom anti-reflective coating platform having improved resolution and processing latitude required for critical micro-touching applications. SUMMARY OF THE INVENTION The present invention relates to the formation of microelectronic structures. The method of claim 5, 2010, 35, 690, which comprises providing a substrate having a surface on which an anti-reflection = is formed, and a photoresist is applied to the anti-reflective layer to form an image-forming layer. The inclusion is dissolved or dispersed in a solvent. The antireflective composition of the crosslinkable polymer in the system forms an antireflective layer. The polymer comprises a cyclic monomer unit having an adamantyl group. The invention also relates to a microelectronic structure comprising a substrate having a surface, and A cured anti-reflective layer adjacent to the surface of the substrate and a photoresist layer adjacent to the anti-reflective layer. The anti-reflective coating composition comprising a copolymerizable polymer dispersed or dispersed in a solvent system forms an anti-reflective coating. The polymer comprises a recycled monomer unit having an adamantyl group. An antireflective coating composition is also provided, which comprises dissolving or dispersing in a solvent system a crosslinkable polymer and a crosslinking agent. The polymer comprises a cyclic monomer unit having a pentacycloalkyl group and a cyclic monomer unit having an acid group. [Embodiment] The present invention relates to a novel bottom anti-reflective coating composition. a method of using the composition, and a structure formed therefrom. The composition such as shawin is preferably insoluble in an organic solvent and a photoresist developer when cured, but can be decrosslinked in the presence of an acid and used as a developer. Removal. In some aspects, the anti-reflective coating composition of the cured cross-linking is decoupled after exposure to radiation followed by peb. In short, the composition is photo-sensitive. In other aspects, the composition Essentially not photosensitive, relying on the acid diffused from another layer (such as a photoresist) during exposure to de-crosslink the cured composition. Under either of the three shapes, this allows the anti-reflective coating to pass through. The exposed portion and the unexposed portion have a 201035690 different/combination rate. The exposed P/7 can be removed without removing the unexposed portion. Therefore, in both cases, the bottom anti-reflective coating composition of the present invention can be used. Wet development.士士 V As used herein, the term "developer soluble or "wet developable" such as *"w as described herein, the composition is soluble in alkaline developer or hide after decrosslinking φ — ^ Α water so that its force is substantially removed by conventional aqueous developer or water. The composition ruthenium comprises a crosslinkable polymer (polymer binder) dissolved or dispersed in a solvent system, and more preferably a thermally crosslinkable polymer. The composition D also preferably comprises a crosslinking agent which is conjugated to or dissolved in the solvent system. In some cases, the composition may also contain a photoacid generator (PAG) and/or a quencher.

The polymer preferably comprises a recycled monomer unit having an adamantyl group. The diamond sulphate may be part of the polymer backbone, or it may be a pendant acetonide group. The (four) alkyl group is preferably attached to the polymer backbone via a linking group such as a brew or ether. The adamantyl group preferably has acid instability (acid decomposability). As used herein, the term "acid labile" or "acid decomposable" adamantyl means that adamantyl is substituted on the carbon (hydrazine; carbon) attached to the linking group of the polymer (eg, , methyl, ethyl, isopropyl or cyanomethyl). The cyclic monomer unit having an adamantyl group preferably does not participate in crosslinking of the polymer during thermal crosslinking. The gold (tetra) group itself is also preferably free of any acid groups (e.g., the absence of a -OH group). Particularly preferred adamantyl monomers for forming a polymer include adamantane acrylate and adamantyl methacrylate, wherein adamantyl methacrylate is particularly preferred and is selected from the group consisting of: 2,4-isopropyl-2-bromide (4) (ιρ 2010 7690 曱 丙 丙 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- (AM), 2-(cyanoindenyl)_2-adamantyl methacrylate (CAM) and 2-[(2-methyl-adamantyl)-oxy]-carbonylmethyl methacrylate (MACM) Preferably, the adamantyl monomer is at least about 1% by weight, more preferably from about 1% by weight to about 60% by weight, and even more preferably, based on the total weight of the polymer as 100% by weight. Amounts of from about 15% by weight to about 55% by weight are present in the polymer. Preferred polymers also comprise recycled monomer units having acid functional groups (i.e., having pendant acidic functional groups). Preferred acid groups are selected. Free group consisting of: hydroxy (-OH)' carboxyl (_C00H), phenolic group (_Ar_〇H), gas alcohol (-C(CF3)2〇H), and mixtures thereof. The pendant adamantyl group preferably does not contain an acid. In the present invention, the cyclic monomer unit having an acidic functional group is preferably a monomer not based on an adamantyl group (i.e., does not contain an adamantyl group). The acid group is preferably at least @3 wt%, preferably from about 4 wt% to about 30 wt%, and more preferably at about: wt%, based on the total weight of the polymer as 1% by weight. An amount of up to about 25% by weight is present in the polymer. Unlike the prior art composition*, the acid group serving as a crosslinking site (or crosslinkable moiety/knife) is preferably protected from the protecting group. That is, at least $ 95% preferably to about 98% 'and preferably about i〇〇% of the acid group is unprotected to prevent the acid group from being active. The thinning group is such that, particularly preferably, the polymer should comprise the following cyclic monomer units , 201035690

Wherein each Ri is selected from the group consisting of -η, branched and unbranched alkyl groups (preferably G-C6 alkyl groups, more preferably Ci_C4 alkyl groups) and cyclic groups (including heterocyclic rings); preferably 3 12 j clothes a group of members, preferably 4_8 ring members; each μ Ο is individually selected from the group consisting of -OH, -L-OH, -CO〇H, -L_C00H, and _L_C(CF3)2〇H, wherein L may be any suitable linking group (Zhc blade and unbranched alkyl group (Ci_Ci〇〇, preferably Ci_C2〇 and more preferably Ci-Ce), aromatic group (_Ar) or decylamine); The R3 is individually selected from the group consisting of:

Each of the R4 groups is individually selected from the group consisting of branched and unbranched alkyl groups (Ci_c4 alkyl group, and preferably C1-C3 alkyl group) and a chaotic base group. The percentage of moles in the polymer is preferably from about 90:10 to about 30:70, and more preferably from about 854 5 to about 60:40. Alternatively, 'as described above' can incorporate an acid labile adamantyl group into the polymer backbone to replace the cyclic monomer unit having a pendant adamantyl group, 戍9 201035690, except for a recycle order having a side-position diamond justification group In addition to the bulk unit, an acid labile acetonide group can also be incorporated into the polymer backbone. Those skilled in the art can incorporate groups such as the following into the polymer via alternative polymerization techniques:

Wherein each R4 is as defined above, with the exception that one of the R4 groups may also be -H' and wherein each R5 group contains a polymerizable functional group. In addition, different monomers that exhibit varying degrees of acid instability sensitivity can be selected. Dyes (e.g., light attenuating moieties or compounds or chromophores) may also be included in the composition. The dye can simply be physically mixed into the antireflective composition' such as by dissolving or dispersing the dye together with the polymer in a solvent' system. When the dye is physically mixed into the composition, suitable dyes include small molecules, and vouchers or t-chromophores (eg, poly(styrene), such as branched poly(4-hydroxystyrene), poly( Vinylbenzoic acid); 3,7-mono-based 2-naphthoic acid, 3,7-di-trans- 2,naphthoic acid (2,3-epoxypropyl) isocyanate (TEPIC); styrene·cis Butene hydride copolymer, 9-decanoic acid; TEPIC linked to hydroxy-benzoic acid; TEPIC linked to cyanobenzoic acid; and mixtures thereof). More preferably, the dye is bonded to a functional group of the polymer, or even more preferably, the dye is directly attached to the polymer primary bond (i.e., its own monomer repeating unit). The dye may also be constructed as a polymer primary bond (ie, as a part of the above-mentioned monomer single 201035690 7L or as a dye in another composition). It is suitable for anti-reflective coatings and derivatives thereof, and It is made of stupid ethylene, phenyl compound, tea, onion, and is regarded as 1〇«重量%^ material connected (4) Zhao instance, ^ ^ 20 # ^ 〇 / 5 ^ 里 / 〇 to about 65% by weight, and even more佳二: The content of % by weight is present in the polymer. Ο sd = 'The polymer is preferably made of a compound selected from the group consisting of Donkey Kong Donkey and methacrylic acid ruthenium b and at least - The first compound is formed by polymerization, and is selected from the group consisting of a styrene-based compound, a two-component compound such as a 4-injection compound, an acryl-based compound, a methacrylic-based compound, a derivative thereof, a derivative thereof, and a combination thereof. a group of compounds.

G may be included in the polymer as an additional monomer in addition to the crosslinking site, which may include: a polyfluorene aromatic functional group, or any latent acid crosslinking group, or other change in the polarity or hydrophobicity of the poly a group, and can be used to change the parent bonding density, hydrophobicity or polarity of the antireflective film to make it more difficult to de-crosslink thin, and/or to make it more hydrophobic in the unexposed areas and to the developer Less sensitive. Suitable single system is selected from the group consisting of: 2_naphthoic acid decyl acrylate vinegar (ΝΑΜΑ), single _2. (methacryloxy)ethyl succinic acid fluorinated alcohol methacrylate and B〇c-oxystyrene ((iv)Μ). If present, the monomers are preferably from about 5% by weight to about 5% by weight, more preferably from about 2% by weight to about 5% by weight, based on the total weight of the polymer (10% by weight). 〇, even more preferably from about 3% by weight to about 2 〇 by weight. /. And preferably present in the polymer in an amount from about 4% to about 15% by weight. Soil 11 201035690 In another embodiment, the polymer particularly preferred for use in the present invention consists essentially of a cyclic monomer unit having an adamantyl group, a recycled second monomer unit having an acid group, and a dye The cycle consists of a third monomer unit. Regardless of the specific example, the polymer is up to about 10% by weight, preferably from about 6% by weight to about 3.6 % by weight, based on the total weight of the 100% by weight antireflective composition, more preferably about From 7% by weight to @32% by weight, and even more preferably present in the antireflective composition at a level of from about 0.8% by weight to about 3% by weight. The polymer also preferably has a weight average molecular weight of up to about g/mQi, more (iv) 2,5〇〇g/m〇1 to about 70,000 g/mol, and even more preferably from about 4,_1 to about 60,000 g/mol. (M). As mentioned above, the composition also preferably comprises a crosslinking agent. A preferred crosslinking agent is an ethylene linkage crosslinking agent. It is especially preferred that the crosslinking agents are polyfunctional fluorene (bifunctional, trifunctional and tetrafunctional) crosslinking agents. Example of a sulphuric acid plant: a vinyl ether sold under the trade name vECTomerTM (Aldrich; St ϋ m〇). A suitable vinyl ether crosslinker can also be prepared as described herein. It is considered to be 100% by weight of the composition. The total weight of the cross-linking agent is preferably from about 5% by weight to about 8% by weight, preferably from about 2% by weight to about 9% by weight, and even more preferably from about 0.25% by weight to A content of about 8 wt% is present in the composition. More preferably, if present, the vinyl ether crosslinker has the formula: 0-CH=zCH2)n wherein is selected from an aryl group (preferably C6_Ci4) and A group consisting of a base (preferably (vc18' and more preferably Cl_Ci〇), each selected from the group consisting of an alkyl group (k仫 is cvc, and more preferably Ci_c), an alkoxy group (preferably 12 201035690

Ci-Ci8, and more preferably Ci-CiG), a plurality of groups, and a combination of the above two or more, and η is at least 2, and preferably 2-6. The preferred vinyl ether comprises a vinyl ether selected from the group consisting of ethylene glycol vinyl ether, trimethylolpropane trivinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and mixtures thereof. Another preferred vinyl ether has a structural formula selected from the group consisting of:

Public

PA Ό 13 13 13 201035690 Preferably, the PAG used in the antireflective composition is selected from the group consisting of strontium salts (eg, triphenyl sulfonium perfluorosulfonate, such as TPS nonafluorobutane sulfonate, TPS) Trifluorosulfonium sulfonate ' TPS sulfonate and its substituted form, such as perfluoro-1-butanesulfonic acid ginseng (4-t-butylphenyl) hydrazine (alkyl substituted TPS hexafluoride) Butyrate) can be purchased from sigma-Aldrich; will be continued from acid (eg '肟-sulfonate sold by CIBA under the name CGI®); triazine (eg 'available from Midori Kagaku TAZ108®); succinimide-based sulfonate (Midori Kagaku); naphthylquinone-based sulfonate (Midori Kagaku); sulfonium salt; and combinations thereof. If present, PA (3 should be from about 0.005 wt% to about 〇.〇8 wt%, preferably from about 〇〇〇8 wt% to about 100 wt% of the total weight of the composition. 〇·〇 7 wt%, and more preferably present in the composition in an amount of from about 0.1% by weight to about 6% by weight. The antireflective composition preferably contains substantially no acid, in some embodiments, Producing agent (PAG or thermal acid generator (TAG)) and thus not photosensitive. That is, the 'anti-reflective coating composition preferably contains less than about 0.01% by weight of acid.

Included, Digestion 14 201035690 Preferably, the quencher used in the composition is a small molecule such as an amine or a poly-I having a base functional group as a part or a side part of the main chain. The quencher (2) selected from the group consisting of: hydroxypiperidine, triethanolamine, triethylamine, tridecylamine, trimethylamine, trilinolamine, triisopropylamine, tritributolamine, triad Tributylamine, di " alkanolamine, tri-n-butylamine, diethanolamine, diethylamine, dimethanolamine, dimethyl dibutyl, diisopropanolamine, diisopropylamine, ditributolamine, di Tributylamine, -

N-butanolamine, di-n-butylamine, ethanolamine, ethylamine, methanolamine, decylamine, isopropanolamine, isopropylamine, tert-butanolamine, tert-butylamine, n-butanolamine, and n-butylamine, t-Boc-oxystyrene/4-vinylpyridine copolymer, any polymer using 4-vinylpyridine as a monomer, and combinations thereof. If a quencher is present, the antireflective coating composition preferably comprises less than about 5% by weight of the quencher, more preferably from about 0.0002% by weight, based on the total weight of the composition as 100% by weight. About 2% by weight of the quencher' more preferably comprises from about 0.00025% by weight to about 0-018% by weight of the quencher\and even more preferably from about 0.0003% by weight to about 〇〇17% by weight of the quencher. The antireflective coating composition may also be substantially free of quenching agents. In such embodiments, the composition preferably comprises less than about 〇〇〇〇i by weight of the quencher, more preferably less than about 0.00005% by weight of the quencher' and even more preferably comprises about 〇% by weight. Quenching agent. Additional ingredients which may optionally be included in the composition include surfactants, adhesion promoters, antioxidants, photoinitiators, diffusion promoters, dissolution inhibitors, and combinations of the foregoing. Regardless of the specific example, by simply dispersing or dissolving the polymer in a suitable solvent system, the 轫 Du ^ L is preferably under ambient conditions and is sufficient to form a cautious

The time of homogenizing the solution is applied to form an anti-reflective coating composition. It is also preferred to disperse any additional ingredients together with the core n1 compound in the solvent system. Preferred solvent systems include a solvent selected from the group consisting of ethyl ester (EL), ethyl quinone-beta &quot;-propanol methyl ether ester (PGMEA), propylene glycol methyl _ (PGME)' Propylene glycol n-propyl scale \<PnP), % ketone, 7-butyrolactone and mixtures thereof. Preferably, the solvent Li, w, and die have a boiling point of from about u 8 c to about i 6 (rc ' and from about 118 t to about 146 ° C. The solvent system should have a solvent system of at least about 90% by weight, preferably from about 965 (four) to about 99.4% by weight, more preferably from about 96 to 9% by weight to about 99 2% by weight, and even More preferably, the composition is preferably used in an amount of from about 97% by weight to about 99% by weight based on the total weight of the composition regarded as 100% by weight, preferably 5 parts by weight, preferably about 0.8% by weight. A solids content of from about 1% by weight to about 5% by weight, and even more preferably from about 1% by weight to about 2.5% by weight. Figure ΗΑ) - - illustrates a method of forming a structure using the antireflective coating of the present invention. In this method, a substrate 1 having a surface is provided. Any microelectronic substrate can be used in the present invention. The preferred substrate comprises a substrate selected from the group consisting of: Shi Xi, Qi, Si〇 2, aluminum, tungsten, Shi Xihua, Kunhua, Wrong, Syria, Nitrogen, 'Shan Butterfly, Black Diamond, Push scale or push stone glass, ion implantation layer, titanium nitride, oxidation, nitrogen oxynitride and a mixture of the above. The method comprises applying a quantitative amount of the antireflective composition of the present invention onto a substrate 10 to form a composition layer 12 on the surface of the substrate 1 . The composition can be applied by any known coating method, wherein a preferred method is from about 75 rpm to about 5 Torr (preferably from about 16 201035690 ΓΡηΐ to about 4, _ rPm, and More preferably, the composition is spin-coated at a speed of from about 〇〇〇 rpm to about 3,500 rpm for a period of from about 20 seconds to about 90 seconds (preferably from about 30 seconds to about 60 seconds). The substrate 1〇 may have a flat surface, or it may include topographical features (vias, trenches, contact holes, raised features, lines, etc.). As used herein, "topography" refers to the degree of curvature or roughness of a structure in or on a surface of a substrate. For example, the substrate i 〇 can include a structure defining a hole including a sidewall and a bottom wall. Accordingly, the method of applying the antireflective composition to the substrate preferably comprises applying the composition to at least one of the sidewalls of the apertures and the bottom wall of the aperture. After the coverage is achieved, the composition layer 12 is then baked to initiate thermal crosslinking of the group to form a solid. Better hung roasting conditions. 125 ° C ' is preferably about 15 (rc to about 2 Torr, and more preferably about 205 to about 205 C ' and even more preferably about 155. 〇 to a temperature of about 18 〇〇c, and lasts about a second to about The period of 90 seconds (preferably about 45 seconds to about seconds). The thickness of the anti-reflective coating 12 after baking is preferably from about 2 〇 ηηη to about 85, more preferably from about 3 〇 nm to about 75 Å. Even better, it is about 32 Cong to about 7 〇 nm, and the most {soil is about 3 3 n in to about 6 5 n rn. Very A jc main 2 ί λ J J 〇 nm right substrate surface 1 〇 a includes morphology Preferably, the anti-reflective coating 12 is coated with substantially the thickness of the substrate to cover the thickness of the substrate. The polymer acid group is a slow acid group and the crosslinked south is 7 In a specific example of a vinyl ether crosslinker, the crosslinked polymer will comprise an acetal linkage of the formula 3 having the following formula:

17 201035690 ^ wherein R is selected from the group consisting of aryl (preferably, about c6 to about Cl2), ^ knife and unbranched alkyl. As described above, the cyclic monomer unit having an adamantyl group preferably does not participate in crosslinking. A 2-layer 12 will be sufficiently cross-linked to render it substantially insoluble in the typical photop/mixture. Accordingly, the coating of the present invention should have a ratio of less than about 5%, preferably less than about 1%, and even more preferably about 〇%, when subjected to a peel test. The peel test involves first measuring the thickness of the cured layer (by taking the average of the measurements at 5 different locations). This is the average initial film thickness. Next, lactic acid ethyl acetate (EL) was applied (-d) to the cured film for 2 sec seconds, followed by spin drying at about 3,000 rPm for about 30 seconds to remove the solvent. The thickness is then measured at five different points on the wafer using an elliptical symmetry method and the average of these measurements is determined. This is the average final film thickness: the amount of peeling is the difference between the initial average film thickness and the final average film thickness. The percentage of peeling is: % peeling: - peeling amount Initial average film thickness 100 &quot; As described herein, the crosslinked layer 12 is also preferably substantially insoluble in a typical photoresist developer. The solubility of the cross-linked anti-reverse (iv) film in the developer is estimated using the same procedures and calculations as described above for the separation test, with the exception of the use of a developer instead of a photoresist solvent. Also at 11 (rc), the joint layer is clarified, and it takes 6 seconds. Then, G.26NTMA_f^ 捣 is applied to the layer for 45 seconds, followed by 5 seconds of deionized water to rinse and rotate. 18 201035690: Dry 1 Any loss of the thickness of the layer is defined as "dark 1". The cured layer will have less than about 5%, preferably less than about 15% = less than about 1%, and even more preferably less than about 8%, more仫.u.«/. and the best about 〇% of the dark loss. ', can be used with the similar process for the peel test 2 wet development. Hundreds first on the 0rie ~ v broadband exposure unit with broadband light to 20 The cured layer was exposed by mJ/Cm. Then the PEB was subjected to PEB for 13 seconds in 13 passages. Then the photoresist developer (〇26 n)

The crucible was applied to the film for a period of 60 seconds&apos; followed by a 5 second deionized water rinse while rotating at 300 rpm, and then spin dried at about 3, rpm for about 3 seconds to remove the developer. The layer thickness was measured again and the development percentage was calculated. The photosensitive anti-reflective coating will preferably have a percent development of from about 95% to about 1%, and more preferably from about 99% to about 100%. In a specific example where the antireflective coating composition is not photosensitive, the % development percentage will preferably be less than about 1.5%, preferably less than about 0.8%, and even more preferably about 〇%. The refractive index (n value) of the cured antireflective layer or coating 12 will be at least about 1.3', preferably from about i.4 to about 2, more preferably from about 145 to about i8, and even more preferably from about 1.5 to About 1.75. The anti-reflective coating 12 also preferably has an extinction coefficient of at least about 〇2, preferably from about 0.25 to about 0.65, and more preferably from about 〇3 to about 〇6, at a wavelength of use (e.g., 193 nm, 248 mn, or 365 nm). (k value). Referring to Figure 1 (B)', a photoresist composition can then be applied to the cured layer 12 to form the imaging layer 14, creating a stack 16. It is then preferably at least about 9 rc, preferably about 100 volts: to about 135. 〇, and more preferably about 10 (rc to about 13 (coating post-baking (pab) of imaging layer 14 at a temperature of rc, for a period of from about 45 seconds to about 19 201035690 75 seconds. It will be appreciated that imaging layer 14 The thickness can be in the range of about 2,000 nm. Preferably, the thickness of the imaging layer 14 is from about ι to about 250 nm, more preferably from about 120 nm to about 24 Å, and even more. Preferably, it is from about 13 Å to about 230 nm, and most preferably from about n 〇 nm to about 225 nm. Suitable imaging compositions include commercially available photoresists (for example, TarF_Pi6 from T〇K, Kawasaki shi, Kanagawa (Japan). _〇〇1; from JSR Micr〇,

Sunnyvale, CA's ARX3001JN, ARX3340J and AM2073J;

Shin-Etsu, SAIL_X_181 of Tokyo (Japan) or any other light-sensitive composition. Where the antireflective coating composition is not optically sensitive in nature (i.e., an antireflective coating containing less PAG), as described in more detail below, suitable photoresist compositions will preferably comprise an acid generator (compare Preferably, it is sufficient to produce an acid sufficient to decrosslink and remove the protecting group from the adjacent antireflective coating to render it soluble in the developer. The imaging layer 14 can be patterned by exposure to light of a suitable wavelength, followed by exposure of the exposed photoresist. More specifically, referring to Figure i(c), the imaging layer 14 is exposed using a mask 18 disposed over the surface of the imaging layer 14. The mask 18 has an open area 丨 8a that is designed to allow radiation (heart) to pass through the mask 18 and contact the imaging layer 14. The remaining solid portion i8b of the mask 18, j3, is again taken to prevent radiation from contacting the surface of the imaging layer 14 in certain areas. The person skilled in the art should be readily aware of the arrangement of the open region 1 〇a and the solid portion 1 Ob based on the desired pattern to be formed in the imaging layer 14 and ultimately formed in the substrate. Advantageously, the same applies to the k-reflective coating 丨2 of the present month when the imaging layer 14 is exposed to radiation (i.e., light). After exposure, the acid is generated by pAG (which is in the 20 201035690 antireflective coating itself or from the photoresist composition) and this acid "decrosslinks" the polymer in the antireflective coating 12. That is, even in the case where the anti-reflective coating is not optically sensitive in nature, the exposed portion of the anti-reflective coating 12 is diffused from the exposed portion of the imaging layer 14 to the adjacent image forming layer 14 after exposure. The acid in the corresponding portion of the antireflection layer 12 becomes a developer soluble. The acid, whether from a photoresist or an anti-reflective coating, causes the bond formed between the polymer in the antireflective coating and the crosslinker to break after thermal crosslinking. For example, when the acid retardant is an acid group on the polymer, the decrosslinking causes the bond (*) having a bond of the formula to be broken:

4 one step to enhance the acid of the polymer is also better to decompose the acid instability

Solubility. The anti-reflective layer 12 "the exposed portion thus contains free adamantane groups which are removed during development. After exposure, it is preferably about 85. It is about 140, more preferably about 9 5 C to about 13 5 C ' and more preferably about 1 〇 s 5 recognizes, J iU5 C to about 13 〇. &lt;3&gt; The imaging layer 14 and the anti-reflective coating 12 are allowed to dry for a period of about 45 seconds to about 75 seconds. Next, the image forming layer 14 and the anti-reflective coating 屌]) / θ are increased by 12 due to the above process, and the soluble exposed portion is brought into contact with the photoresist developer to remove the exposed portions. While the imaging layer 14 is being removed, the exposed portion of the anti-reflective coating 12 under the exposed portion of the imaging layer 14 is also removed by the developer to form the imaging layer 14 and the anti-reflective coating. In the 12th, the same guilty man ^ J formed the desired pattern 20. Figure 21 201035690 Case 20 can be a via, trench, line, gap, etc., which will eventually be transferred to substrate 10 using an etch or ion implantation process. Preferably, at least about 95% of the exposed portions of imaging layer 14 and anti-reflective coating 12 are removed by the developer, more preferably at least about 99% of the exposed portions are removed, and even more preferably about 100% removed. The exposed portion. Suitable developers are organic or inorganic alkaline solutions such as potassium hydroxide (KOH) 'TMAH, and preferably comprise an aqueous solution of TMAH having a concentration of 〇·26 N or lower. Some of these developers are available under the tradename pd523ad (available from Moses Lake Industries, Moses Lake, WA), MF-319 (available from Shipley, Massachusetts), MF-320 (available from Shipley), and NMD3 (available Purchased from TOK, japan). In another embodiment, the photoresist can be patterned using ArF impregnated lithography (not shown). The medium through which radiation passes during exposure is liquid rather than air (as in conventional lithography). The imaging layer is exposed to radiation via an optical projection element (i.e., through) of the lithography system, wherein the impregnation liquid contacts at least a portion of the optical element of the lithography system and a portion of the structure (i.e., the stack). Even more preferably, the space between the last optical element in the liquid filling system and the imaging layer is such that the optical element is immersed in the liquid. Suitable for immersion &gt; preferably has a refractive index greater than 丨 (preferably from about 1 to about 2, and more preferably from about 1 3 to about 1.4) and is selected from water (preferably pure water) or organic a group of solvents. Immersion lithography systems are known in the art and include from AmphibianTM Systems (Rochester, NY)

Amphlbian interferometer and 1900i from ASML ( Veldhoven, Netherlands). 22 201035690 Regardless of the specific example, etching, metallization, etc. can be performed on the patterned stack to complete device fabrication. If multiple exposure systems are desired: the exposure-development process can also be repeated using a second layer applied adjacent to the patterned anti-reflective coating. EXAMPLES The following examples illustrate the process of the invention. However, it should be understood that the present invention is not limited by the scope of the present invention. x Example 1 Synthesis and precipitation of binary copolymer I

In this procedure, a terpolymer was synthesized using 12-9 mol% of IPM, methacrylic acid and styrene, and then precipitated. 9.08 g (105.5 mm 〇l) methyl methic acid (Sigma-Aldrich, St. Louis, MO), 12,38 g (118 9 mmol) styrene (Sigma-Aldrich, St. Louis, MO), 8.71 g (33 2 mmol) Adamantate® XM-105 (IPM; Idemitsu K〇san Co., Ltd., Tokyo, Japan) and 203.72 g of PGME were placed in a 500 ml three-necked flask equipped with a magnetic stir bar and thermometer. The mixture was stirred at room temperature for 5 minutes to prepare a solution. A dropping funnel with a nitrogen inlet adapter and a condenser with a nitrogen outlet adapter were then attached to the flask. 23 201035690 0.68 g ( 4.14 mmol ) 2,2,-azobisisobutyronitrile (AIBN; Sigma-Aldrich, St. Louis, MO) and 67.63 g PGME were loaded into a transparent 125 ml Nalgene bottle in. The mixture was inverted at room temperature for 0.60 hours to prepare a solution. The AIBN solution was charged into a dropping funnel attached to the flask, and then the reaction system was purged with nitrogen at room temperature for 2. hr. Next, the flask was immersed in an oil bath at l〇2.5t-103°C. The reaction mixture was stirred under nitrogen. The AIBN solution was gradually added to the reaction flask over a period of 3 minutes while the temperature of the reaction solution reached 1 〇3. The resulting reaction mixture was then stirred at 98 ° C - 1051 under nitrogen for 24 hours.产里.299.5 g solution (99% recovery); ι〇·ΐ8 wt.% polymer solids. The terpolymer j in the solution was determined by gel permeation chromatography (GPC) to be 15,150 g/mol, and the dispersibility (D) was 2.8. To precipitate the terpolymer I from the solution, 2 liters of hexane was charged into a 4 liter beaker equipped with a cantilever stirrer and a stir bar. A 2〇〇7笆 IPM terpolymer solution was charged into the dropping funnel, which was then added dropwise from the funnel to the stirred hexane for 5 hours. The mixture was again searched at room temperature for 5 minutes and then allowed to precipitate. The solvent was removed by vacuum transfer. Then, mix the terpolymer solid together with 200 ml of fresh hexane for 2 minutes, then remove the solvent by vacuum. The terpolymer solid was stirred again with 2 Torr and fresh hexane for 5 minutes, followed by removal of the solvent via vacuum transfer. The terpolymer (4) was dried in a (iv) vacuum box, ground into a powder using a mortar and pestle, and dried to constant weight in a 4 (TC vacuum oven. Yield: 126 powder (yield: 62%). Measured by GPC: τ元丑# &amp;^. The Mw of the δ 卞-兀 copolymer is ι6, 〇5〇g/mol ' and 〇 is 21. 24 201035690 Example 2 Preparation of Bottom Resistance Using Terpolymer I Reflective Coating In this procedure, a terpolymer # (IPM, from Example 1 above) and PAG and a quencher were used to prepare the bottom anti-reflective coating. 〇.7 i 8 g internal vinyl ether crosslinker (See Example 27), 2.423 g of terpolymer I, 156.1861 g of PGME and 39.36 g of PGMEA were placed in a 250 ml amber Nergi bottle. The mixture was inverted at room temperature for 152 hours. Next, 1.2596 g of 1% was added. Quencher (i_B〇c_4_hydroxypiperidine; sigma Aldrich st. Ο ,

Louis, MO) PGME solution, followed by 0.0423 g CGI TPS-Cl (Ciba, Tarrytown, NY). The bottle was then inverted overnight at room temperature and the contents were filtered twice through a 〇·1 hiro m end filter and placed in four 6 〇... broken Neldi bottles. The various properties of the resulting bottom anti-reflective coating were then tested. For optical and film properties testing, the bottom anti-reflective coating is first applied to the Shixi wafer with i, 5 paws for 3G seconds or (9) seconds, and it is thermally cured (ie, at 160 C). Bake for 60 seconds). The Gaertner ellipsometry was used to measure and record the initial thickness of the resulting film. To test the solvent resistance of the layer, a photoresist solvent (ethyl lactate) was applied to the film for 2 seconds, followed by spin drying at about 3, GGG rpm for about 3 seconds to remove the solvent. The thickness is then measured using ellipsometry and the percent peel or swell is calculated as described above. The effect of the photoresist developer (〇·26 N TMAH aqueous solution) on the unexposed dark loss coating was also measured. To estimate the dark loss, the other wafer was coated with a reflective coating and flooded as described above, and the initial film thickness was measured and recorded at 25 201035690 degrees. The unexposed layer was subjected to PEB under lure for 6G seconds. The photoresist developer (0-26NTMAH) was then applied to the film, corrected for seconds, then rinsed with deionized water for 5 seconds and spin dried. The thickness of the layer was measured using ellipsometry and the dark loss was calculated. For the EL peel test or dark loss, a positive number indicates that the film is swollen. Next, J_A·w〇〇llam VASE8 ellipsometer 3 was used under 193 _: the η and k values of the film were measured. The film and optical properties of this bottom anti-reflective coating are shown in the results of Example 1 _ 17 of Table 2. A comparison curve of this bottom anti-reflective coating was measured using an OrielTM Duv exposure unit where light was passed through a 248 nm bandpass filter prior to exposure. The bottom anti-reflective coating was spin coated onto the tantalum wafer at MOO rpm for 3 seconds or 60 seconds and baked at 16 (TC for 6 seconds). Exposure of 2 wafers followed by PEB at 100 C For 60 seconds, or at 12 (the PEB lasts 60 seconds, the person, the 951 nm thickness is coated with the anti-surname agent (arx3〇〇1 jn; JSR Micro)' and then the pAB duration is performed at li〇°C 6 sec, exposure, and PEB for 6 sec at 1HTC. The results of the comparison of the two PEBs in the presence and absence of resist are shown in Figure 2(a)-(c). The reflective coating gives the lowest E 底部 of the bottom anti-reflective coating shown in Figures 2(a)-(c). Next, as indicated in Figure 3, on the Amphibian XIS interferometer (Amphibian Systems), various The exposure time was used for 193 nm exposure using lithography covering the resist (ARX3001JN), where PAB and PEB were performed for 60 seconds at 11 。. 150 nm L/S (1:1) was out of range 26 201035690 ' Example 3 Preparation of a bottom anti-reflective coating containing less PAG using Di 70 Copolymer I In this procedure, in the absence of PAG or quencher, use ternary A bottom anti-reflective coating was prepared from Polymer I (IPM). 1 si% g binary oligomer I, 0.359 g crosslinker (from Example 27), 74.3〇9 g pQME, and 19.679 g PGMEA were loaded into i25 In amber amber Nerki bottle, the compound was turned over overnight at room temperature, and then filtered using an 〇. 1 filter for end point filtration. The resulting bottom anti-reflective coating was spin coated onto the wafer under the following rotation parameters. Top: a) 丨, 5 rpm, lasts 30 seconds or 60 seconds, or b) at 2,738 rpm' for 30 seconds or 60 seconds, after each condition is baked at 16 〇t:T for 60 seconds. The rotation parameter a) gives a thermoset bottom anti-reflective coating of 54 nm-55 nm, while the rotation parameter b) gives a 38 nm thermoset bottom anti-reflective coating. Next, as described above in Example 2, a 193 nm lithography was performed using a blanket resist ARX3001JN at a thickness of 1 95 nm. SEM photographs (made using LEO 1560 from Carl Zeiss SMT) are shown in Figure 4. For both thicknesses, excellent i 5 〇 nm L/S (1:1) is obtained.薄膜 The film and optical properties of the bottom anti-reflective coating were then determined as described above in Example 2. The results are shown in Table 2. Example 4 Synthesis and Precipitation of Metapolymer II

27 201035690 In this procedure, three 7L copolymers were synthesized using 12.9 m〇i〇/0 EM, mercaptoacrylic acid and styrene. 9.1 g (1〇6 mmol) of methacrylic acid, 12.40 g (119.15 mmol) of ethylene, 8.26 g (33.3 mmol) of Adamantate® EM (Idemitsu Kosan Co., Ltd., T〇ky〇, Japan) and 2〇〇·78 Lu PGME was placed in a 5 〇〇 ml three-necked flask equipped with a magnetic stir bar and a thermometer. The mixture was stirred at ambient temperature for 6 minutes to obtain a solution. A condenser with a nitrogen outlet adapter and a dropping funnel with a nitrogen inlet adapter were attached to the flask.

Next, 0.654 g (3.98 mm 〇l) AIBN and 66.88 g PGME were placed in a 125 ml Nerji bottle. The mixture was inverted at room temperature for 6 hours to prepare a solution. The hydrazine solution was then transferred to a dropping funnel. The reaction system was purged with nitrogen for 15 minutes, and then the flask was immersed in an oil bath at 1 Torr. At 98 C-104. . The mixture was stirred under nitrogen for 24 hours. Yield: 294.4 g solution (99% recovery); 1 〇 18% polymer solids 'measured by GPC, the core of the copolymer in the solution was 15,25 〇 _〇1, and the enthalpy was 2.5. To precipitate the terpolymer from the solution, 2.00 liters of hexane was charged, 4 liters: in a cup. 199.8 g of the terpolymer π solution was placed in a dropping funnel and then added dropwise thereto at a temperature of 13.2 minutes until it was stirred, and the mixture was mixed and heated for 6 minutes. The solvent was removed by vacuuming. About 200 ml of fresh broth was added to the terpolymer as a washing solution, and the mixture was further stirred for 6 minutes. Then, the mixture was removed by vacuum filtration, and then 200 ml of fresh hexane was added thereto, and the mixture was stirred for 5 minutes. Then 28 201035690 Remove the solvent by vacuum filtration. The terpolymer was dried to constant weight in a 4 (TC vacuum oven. Yield: 14.0 g (69% recovery). The Mw of the terpolymer was measured by GPC to be 16,850 g/mol, and D was 2.1. Example 5 Preparation of Bottom Anti-Reflection Coating Using Terpolymer II In this procedure, a terpolymer anti-reflective coating was prepared using a terpolymer Π (EM, from Example 4 above), PAG, and a quencher. 535.5353 g PGME solution from the crosslinking agent of Example 27, 1.8215 g terpolymer Π, 1171579 〇g PGME, 29.5210 g PGMEA, 0_9456 g 1 % quencher (υκ hydroxypiperidine) and 0.0316 g TPS -C1 was charged into a 25 0 ml Nerki bottle. The mixture was inverted overnight and then filtered through a 〇.丨ηηι end filter. The ternary anti-reflective coating of the terpolymer η was then determined as described above in Example 2. Film and optical properties. The results are shown in Table 2. The comparative curves of the terpolymer π bottom anti-reflective coating were also determined as described above in Example 2 and are shown in Figure 2. Next, as above 193 nm lithography was performed as described in Example 2. For each exposure time, SEM photo (Prepared using Carl Zeiss SMT's LEO 1560) is shown in Figure 3. As shown in Figure 3, 150 nm L/S was obtained from a 1.2 second exposure at a film thickness of 52 nm - 5 6 nm (1: 1) Example 6 Preparation of a bottom anti-reflective coating containing less PAG using terpolymer II In this procedure, in the absence of PAG or quencher, terpolymer II (EM, from implementation) Example 4) Preparation of a bottom anti-reflective coating. 29 201035690 0.359 g of crosslinker from Example 27 '78.715 g PGME, 19.676 g PGMEA, 1.214 g terpolymer II were placed in a 250 ml amber Nergi bottle The mixture was inverted at room temperature for 3 · 5 hours or more. The coating was then filtered through a 私 1 private claw end filter. The film and optical properties of the anti-reflective coating were determined as described above, followed by 193 nm lithography. The film and optical properties of this bottom anti-reflective coating are shown in Table 2. SEM photographs are shown in Figure 5. Example 7 Terpolymer III Synthesis and Precipitation

In this procedure, a terpolymer of 12.9 mol 〇/〇 AM, methacrylic acid and stupid ethylene was used. 9.07 g (105.4 mmol) of methacrylic acid, 12.37 g (118.8 mmol) of styrene, 8.32 g (33.2 mmol)

Adamantate® M-101 ( AM; Idemitsu K〇San Co., Ltd., T〇ky〇,

Japan ) and 200.94 g PGME were placed in a 500 ml three-necked flask equipped with a magnetic stir bar and a thermometer. The mixture was stirred at room temperature for about 3 minutes. A condenser connected to a nitrogen outlet adapter and a dropping funnel connected to a nitrogen inlet adapter were connected to a three-necked flask.

Next, 0.68 g ( 4.14 mm 〇l) AIBN and 54 595 g pGME were placed in a 60 ml Nerji bottle. The mixture was inverted for 2 hours at room temperature to make 30 201035690

The solution was formed and the solution was then added to the dropping funnel. About 12 丨丨g of PGME was added to 6 〇 ml of the ergo-abandoned tile to thoroughly rinse the inside of the bottle, and this rinsing liquid was also added to the dropping funnel. The reaction system was purged with nitrogen for 15 minutes at room temperature and then at 99.5. . The flask was immersed in an oil bath. The reaction mixture was stirred under a nitrogen atmosphere. The rhodium solution was added dropwise to the flask over a period of about 3 minutes at a temperature of the reaction solution of 1 〇 2 $ π. The reaction mixture was thundered under nitrogen at about 97 ° C - 105 ° C for 24 hours. Yield: 295.4 g solution (99% recovery); 1 〇 17% solids. The Mw of the terpolymer III in the solution was determined by Gpc to be 18'65 〇g/m〇l, and D was 2 & To precipitate the terpolymer from the solution, 2 liters of hexane was charged into 4 Lit in the beaker. Approximately 199.9 g of the terpolymer m solution was added dropwise to the stirred hexane over 5 hours. The mixture was then stirred at room temperature for 5 minutes. The solvent was removed from the terpolymer solid using vacuum filtration. At room temperature, the binary copolymer solids were mixed with fresh 2 〇〇 mi for 5 minutes and the solvent was removed by a vacuum transition. An additional 200 ml of hexane was added and then mixed for 5 minutes. The solvent rinse was removed by vacuum filtration. The terpolymer was dried in a 4 ° C vacuum oven, ground to a powder using a mortar and pestle, and then at 4 Torr.真空 Vacuum to dry the phase to constant weight. Yield: 15.4 g (76% recovery). The ternary copolymer in the river was evaluated as 19,15 〇 g/m〇1 and D was 23 by GPC. Example 8 Preparation of a bottom anti-reflective coating using a terpolymer ruthenium In this procedure, a bottom anti-reflective coating was prepared using the terpolymer AM (AM), PAG and quencher from Example 7. ο.? 1 5 g of the crosslinker of Example 27, 2.421 g of terpolymer ΠΙ, 丨57.06〇 g 31 201035690 PGME and 39.54 g of pGMEA were weighed into a 250 ml amber Nerki bottle. Then 'add about 1 256 g of 1% quencher (&gt; 4_hydroxypiperidin) to the PGME solution, followed by 0.0427 g of TPS-C1. The mixture was inverted overnight at room temperature and then passed through. The μπ1 endpoint filter was filtered. The film and optical properties of the terpolymer in the bottom anti-reflective coating were then determined as described above in Example 2 and provided in the results in Table 2 below. The ternary copolymer was determined as previously described. A contrast curve of the anti-reflective coating on the bottom of the material, and is shown in Figure 2. Next '1 93 nm lithography was performed as described above in Example 2. The SEM photograph from Figure 3 can be seen at 1.2 seconds and 1.4 After exposure to a second, it exhibits 150 nm L/S (1:1). Example 9 Synthesis and precipitation of terpolymer IV

In this procedure, a terpolymer was synthesized using 12.9 mol% CAM, methyl acrylate, and styrene. 8.59 g (33.1 mmol) Adamantate® M-102 (CAM; Idemitsu Kosan Co., Ltd., Tokyo, Japan), 9·10 g (105.7 mmol) of methacrylic acid, 12.38 g (118.9 mmol) of styrene and 202.70 g of PGME Into a 500 ml three-necked flask equipped with a magnetic stir bar and a thermometer. The mixture was stirred for 2 minutes to make a solution. A condenser connected to a nitrogen outlet adapter and a dropping funnel connected with a nitrogen inlet adapter 32 201035690 were attached to a three-necked flask. Next, 0.65 g (3.96 mmol) of AIBN and 54.91 g of PGME were placed in a 60 ml Nerji bottle. The mixture was inverted at room temperature for 5 hours to obtain a solution. This solution was added to a dropping funnel. The Nergi bottle was rinsed with approximately 12 丨 9 g PGME and the PGME rinse was added to the dropping funnel. The reaction system was blown with nitrogen for 15 minutes and then at 1 〇 3.5. The flask was immersed in an oil bath under the armpit. The reaction mixture was stirred under a nitrogen atmosphere. The AIBN solution was added dropwise to the calcined bottle over about 3 minutes while the temperature of the reaction solution reached 101 · 5 °C. At 97. 〇106. (: Next 'The reaction solution was stirred under nitrogen for 24 hours. Yield: 295.9 g solution (98.5% recovery); 10.19 wt.% polymer solid. The Mw of the terpolymer iv in the solution was determined by GPC to be 14,850 g/ Mol ' and d is 2.6. To precipitate the terpolymer from the solution, 2 liters of hexane was charged into a 4 liter beaker equipped with a cantilever stirrer. 200.0 g of terpolymer IV; In a dropping funnel, the terpolymer solution was added dropwise to the stirred hexane over 17 minutes, and then the mixture was stirred at room temperature for another 7 minutes, and then the solvent was removed by vacuum filtration. 〇ml fresh hexane was added to the flask, followed by stirring for 7.5 minutes, and the solvent was removed by vacuum filtration to repeat the process. For the final rinse, 200 ml of hexane was added to the terpolymer solid, and the mixture was stirred. The solvent was removed by vacuum filtration for 8 minutes. The terpolymer was dried in a 4 (TC vacuum oven), ground to a powder using a mortar and pestle, and then dried in vacuo at 4 CTC to constant weight. Yield: 14.0 g (69% recovery rate measured by GPC The copolymer Μ* is 14,950 g/mol and D is 2.2. 33 201035690 Example 1 ο Preparation of a bottom anti-reflective coating using terpolymer IV In this procedure 'Use terpolymer IV (CAM, from The above Example 9), PAG and quencher were used to prepare the bottom anti-reflective coating. 〇·3585 g of the cross-linking agent from Example 27, 0.6335 g of 1.001% quencher (i-Boc-4-Zhaoji B) The PGME solution, 1 _2 1 3 g terpolymer IV, 78.0985 g PGME and 9.687 g PGMEA were charged into a 125 ml amber Nerki bottle. The mixture was inverted at room temperature for 33 minutes, followed by 20.9. Mg tps-ci. The mixture was inverted at room temperature for about 72 hours and then filtered through a 过滤μηι end filter. The film and optical properties of the resulting bottom anti-reflective coating were then determined as described above in Example 2, and It is provided in the results in Table 2. Next, 193 nm lithography was performed using the anti-reagent ARX3 001JN at a thickness of 1 95 nm as described above in Example 2. The SEM photograph is shown in Figure 6. Example 11 Ternary copolymerization Synthesis of V and its precipitation

In this procedure, a terpolymer of 12.9 mol% MACM, methacrylic acid and styrene was used. 9.09 g (1 05.6 mmol) methacrylic acid, 9.70 g (33.2 mmol) Adamantate® M-103 (MACM; Idemitsu 34 201035690

Kosan Co., Ltd., Tokyo, Japan), 12.365 g (118.7 mmol) of stupid ethylene and 209.93 g of PGME were placed in a 500 ml three-necked flask equipped with a thermometer and a magnetic stir bar. The mixture was stirred at room temperature for 3 minutes. A dropping funnel with a nitrogen inlet adapter and a condenser with a nitrogen outlet adapter were attached to the flask.

Next, 0.650 g (3.96 mmol) of AIBN and 69.65 g of PGME were placed in a 125 ml Nerki bottle. The mixture was inverted for 65 hours to prepare a solution, which was then charged into a dropping funnel. The reaction system was purged with nitrogen at about room temperature for 0.4 hours, and then at 99.5. (The flask was immersed in an oil bath. The reaction mixture was stirred under nitrogen. The AIBN solution was passed through 2 75 reaction solution under the flow of the stirred solution to a temperature of 2 ° C and nitrogen flow. , in a nitrogen atmosphere for 24 hours. Yield: 308·5 g solution (99% recovery); 10.18 wt % polymer solids. The terpolymer Μ* in the solution was determined by GPC to be 17,900 g/mo b and d 2.6. 使$ The precipitate was precipitated from the solution, and 92.0 g of the terpolymer v solution was placed in the dropping funnel, and the milk ml was shaken into a 1 liter beaker equipped with a cantilevered whip. The terpolymer solution was added dropwise to the broth in 8.5 minutes, followed by G. 2 hours, and then the solvent was removed by Shikong filtration. By adding about 85 ml of home. The ternary copolymer was rinsed into a beaker and stirred at a temperature of 5 minutes. The solvent was removed by vacuum filtration. The process was repeated using 87 ml of fresh γ γ 3 / p, w &quot; by 真二::下下12 The solvent is removed in an hour. The dry m in the vacuum oven is used to grind the powder into a powder, and 35201035690 vacuum oven dried to constant weight Yield:. 7 · 28 g (78% recovery) as measured by GPC of the terpolymer v] ^ was 17,900 g / mol, and D is 2 2〇 Example 12.

Preparation of a bottom anti-reflective coating using terpolymer V In this procedure, a bottom anti-reflective coating was prepared using a terpolymer V (MACM, from Example Π), PAG, and a quencher. 〇·535 g of the crosslinker from Example 27, 丨.812 g terpolymer v, 117131 gp (jME and 29.517 g PGMEA were placed in a 250 ml amber Nel base bottle. The mixture was turned over at room temperature. 2.1 hours, followed by the addition of 〇·943 g 1〇〇1 wt% quencher (1-Boc-4-hydroxypiperidine) to the pGME solution. The mixture was inverted at room temperature for 0.5 hours. Then 32 〇mg Tps was added. Ci. The product was inverted at room temperature for about 72 hours and filtered through a 〇·丨μηι endpoint filter. The film and optical properties of the resulting bottom anti-reflective coating were determined as described above in Example 2 and provided below. In the results of Table 2. Example 13 Synthesis and precipitation of diterpene copolymer VI

In the bottle. 12·9 mol% butyl methacrylate, a traditional acid unstable terpolymer for 8 mmol) methacrylic acid, 135 g (94.9 7 g (339.6 mmol) styrene gel stir bar, thermometer, Three neck burning with outlet condenser

In a separate container, 36 201035690 A was mixed with 168,3 g PGME to form a solution. Add a solution to the dropping funnel. The reaction system was purged with nitrogen under ambient conditions for 15 minutes and then under nitrogen, under mixing, at about. [The flask was immersed in an oil bath t. When the temperature of the reaction solution reached 縦 (3), the mash was added from the dropping funnel at a rapid drip rate. In the reduction of τ, the (four) mixed character is maintained at about 1 (24 hours). The ternary in the solution is measured by GPC: the Mw of the polymer VI is 17,900 g/mol, and d is 2 5 - for the ternary The copolymer precipitated from the solution, and a portion (referred to as a terpolymer VI solution was added to a 4 liter flask equipped with a stir bar and containing about wo as a hexane. The ternary copolymer adhered to the bottom of the flask, thus pouring out The mixture was burned and the terpolymer was collected in another crucible. The precipitation was repeated using the remaining polymerization solution. After the remaining terpolymer was immersed in the solution, the material was washed twice with hexane. At room temperature in i The terpolymer was dried in a liter beaker for 1 hour, and then placed in a 5 (rc vacuum oven and dried. The ternary copolymer ¥1 was measured by GPC to be 19,6 〇〇g/m. 〇i, and D is 2.1. Example 14 Preparation of a bottom anti-reflective coating using a binary copolymer VI In this procedure, a bottom anti-reflective coating was prepared using the terpolymer VI, PAG and quencher from Example 13. 。_2136 g terpolymer VI, 0.3588 g of crosslinker from Example 27, 78 72 〇g P (3ME 19.680 gPGMEA, 0.0063 g quencher (i_B〇c_4_hydroxypiperidine) and 0.0213 g TPS-C1 were charged to the vessel. The mixture was stirred at room temperature to make a solution which was then passed through a 0.1 endpoint filter. 37 201035690 The film and optical properties of the resulting bottom anti-reflective coating were then determined as described above in Example 2 and provided in the results of Table 2 below. The terpolymer III bottom anti-reflective coating was determined as previously described. The curves are compared and are shown in Figure 2. Next '193 nm lithography was performed as described above in Example 2 and the results are shown in Figure 3. Example 15 Terpolymer VII Synthesis and Precipitation in this Procedure A binary copolymer was synthesized using 2 1.9 mol% EM, methylpropionic acid and styrene. 17.72 g (71.3 mmol) Adam antate® EM, 15.84 g (15 2.1 mmol) styrene, 8.80 g ( 102.2 mmol) methacrylic acid and 267.66 g PGME were placed in a 500 ml three-necked flask equipped with a magnetic stir bar and a thermometer. A condenser with a nitrogen outlet adapter and a dropping funnel with a nitrogen inlet adapter were connected to On the flask.

Next, 0.837 g (5.10 mmol) of AIBN and 89.196 g of PGME were placed in a 1 2 5 ml Nerki bottle. The mixture was allowed to dissolve at room temperature until it was added to the dropping funnel. The reaction flask was immersed in an oil bath at 105T:. When the temperature of the reaction solution reached about 1 〇 〇 C, the AIBN solution was added at a rapid dropping rate. The reaction mixture was maintained at this temperature for 24 hours and then allowed to cool. The Mw of the terpolymer VII in the solution was determined by GPC to be 1, 3,300 g/mol, and D was 2.3. A portion (about 380 g) of the terpolymer VII solution was precipitated in 1,900 ml of hexane. The terpolymer was rinsed 3 times with about 50 ml hexane aliquots and then dried in a 40 ° C vacuum oven. Yield: 16.65 g (approximately 44% 38 201035690 recovery). The Mw of the terpolymer VII was measured by GPC to be 15,700 g/mol, and D was 1.7. Example 16 Preparation of a bottom anti-reflective coating using terpolymer VII In this procedure, a terpolymer VII (21.9 mol% EM from Example 15), PAG and a quencher were used to prepare a bottom anti-reflective coating. Floor. 1.2129 g terpolymer VII, 0.360 g of the crosslinker from Example 27, 78.08 g PGME, 19.67 g PGMEA, 0.639 g 1% quencher (lB〇c-4-hydroxypiperidine) in PGME solution, And 0.0220 g of TPS-Cl was placed in the container. The mixture was stirred at room temperature to make a solution, and then it was filtered through a 0.1 μm end filter. The results of the measurement of the film and optical properties of the terpolymer νπ bottom anti-reflective coating as described above in Example 2 are shown in Table 2. A comparative curve of the terpolymer VII bottom anti-reflective coating was also determined as described above in Example 2 and is shown in Figure 2. Example 17

G Preparation of a bottom anti-reflective coating containing less PAG using terpolymer VII In this procedure, a bottom anti-reflective coating was prepared using the terpolymer VII from Example 15 without PAG or quencher. Floor. 12133 g of the binary copolymer VII, 0.183 g of the crosslinker from Example 27, 68.679 g of PGME and i7_169 g of PGMEA were charged into a 125 (6) amber Nerki bottle. The mixture was inverted at room temperature for 4.1 hours and then passed through a 〇.丨ηηι end filter transition. 39 201035690 The resulting bottom anti-reflective coating was spin coated onto a crucible wafer at 1 500 rpm for 30 seconds or 60 seconds and baked at 160 ° C for 60 seconds resulting in a film thickness of 53.3 nm. For this bottom anti-reflective coating, the 193 nm lithography obtained using the anti-surrogant ARX3001JN and PAB/PEB 60 seconds at 110 °C is shown in Figure 7. Examples 1-17 Results In Examples 1-12 and 15-17, conventional acid labile monomers, such as the third butyl ester (see Examples 13 and 14), which are high activation energy groups, are replaced. It is an adamantyl methacrylate monomer which requires a lower activation energy. If the acid labile monomer accounts for only a small percentage of the total polymer, this minor change will result in significant and unexpected changes in the following aspects: 1) Comparison curve and scavenging dose of the bottom anti-reflective coating obtained ( Dose-to-clear, E〇); and 2) The effectiveness of the bottom anti-reflective coating in the 193 nm lithography. Table 1. Description of terpolymers Identity of terpolymers Acid instability Monomer percentage of monomeric acid labile monomers (when loaded) Percentage of moles of AIBN (when loaded) Percentage of recovery of polymerization solution Percentage of yield of precipitated in alkane. Molecular weight of terpolymer (Mw/D) I IPM 12.9 1.6 99 62 15,150/2.8 (solution) 16,050/2.1 (precipitate) II EM 12.9 1.5 99 69 15,250/ 2.5 (solution) 16,850/2.1 (precipitate) III AM 12.9 1.6 99 75 18,650/2.6 (solution) 19,150/2.3 (precipitate) IV CAM 12.8 1.5 98 69 14,850/2.6 (solution) 14,950/2·2 (precipitate ) V MACM 12.9 1.5 99 78 17,900/2.6 (solution) 17,900/2.2 (precipitate) VI Burnt ester 12.9 1.5 - ~68 17,900/2.5 (solution) 19,600/2.1 (precipitate) EM 21.9 1.5 - ～44 13,300/2.3 (Solution) 15,700/1.7 (precipitate) 40 201035690 Table 2. Bottom anti-reflective coating film and optical properties Bottom anti-reflective coating terpolymer film thickness, run EL peeling __ --- development, unexposed areas (dark loss) 193 nm n/k Example 2 I 53.0 +0.5% +0.0% 1. 69/0.54 Example 3 I 54.0 +0 47% +0.21% 1.69/0.54 Example 5 Π 53.9 +1.3% +0.2% 1.70/0.54 Example 6 Π 47, 8 +0.96% +0.58% 1.68/0.54 Example 8 卜m 52.8 ^ +0.4% +0.0% 1.68/0.51 Example 10 IV 54.4 +0.4% +0.3% 1.67/0.51 Example 12 V 52.6 +0.8% +18% 1.72/0.48 Example 14 VI 56.4 + 0.9% -0.8% 1 68/0.56 Example 16 νπ 53.5 +0.4% -1.5% 1.69/0.49 〇Example 1 8 Using a terpolymer I and a polymeric amine additive to prepare a bottom anti-reflective coating containing less pAG This procedure, using a terpolymer I (IPM) from the above Example 1 and a polymeric amine additive (quencher) to prepare a lower Q antireflective coating. 〇.536 g of the crosslinker from Example 27, 4-ethylene ratio bite to t-Boc-oxystyrene (i:im〇i) 〇52 mg copolymer (internal synthesis), 116.710 g PGME 29.186 g PGMEA and 1.871 g terpolymer I were placed in a 250 ml amber Nerki bottle. The /3⁄4 compound was inverted at room temperature for 17 hours to give a solution, which was then filtered twice with a 〇·1 end-pointer. The resulting bottom anti-reflective coating was spin coated onto a tantalum wafer at 1,500 rpm for 60 seconds and then baked at 16 (rc for 6 seconds). The optical and film properties of the resulting bottom anti-reflective coating were as described above. The procedure of Example 3 (no 41 201035690 amine additive) prepared with less PAG terpolymer The properties of the bottom anti-reflective coating are provided in Table 3. For 193 nm lithography, the resistance is at L50Q rpm. The reflective coating was spin-coated onto the crucible wafer for 30 seconds, then at 6 〇 and baked for 6 seconds. The resulting film had a thickness of about 52 nm. The coated photoresist (arx3001jn, at 19 〇 nm), The pAB was then carried out under iurc for 6 sec. Exposure was performed using an asml 1100-ArF scanner, followed by pEB at i 〇 6 &lt; t for 60 seconds. The exposure conditions are shown below. Ring 0.75 Illumination Mode - NA- 0.85/0.57 Target CD-Development-aTMAH '130 nm L/260 nm P (bright field) OPD262A, 45 seconds ARCH semiconductor chemistry as shown in Figures 8(a) and 8(b), 130 nm dense ( 1:1) and isolated line exhibitions are not almost undercut. For dense lines and orphans at an exposure dose of 27 mJ/cm2 The focal depth of both lines (Depth_〇f_f〇cus, d〇f ) is about 0.3 μη. The gap is removed 'except for some resist microbridges observed in dense patterns. This bottom anti-reflective coating is used for display. The potential for even smaller CDs. Example 1 9 Synthesis of adamantyl polymer including ruthenium in this procedure 'by the fourth monomer 2-naphthoic acid-3-mercapto acrylate cool (ΝΑΜΑ) A novel polymer solution was prepared by incorporating 14 wt.% of the monomer mixture into the terpolymer I binder. 9.99 g (1〇5 6 mm〇l)曱42 201035690-based acrylic acid '10.56 g (101.4 mmol) styrene, 8.72 g (33.2 mmol) Adamantate® M-105 (IPM; Idemitsu Kosan Co., Ltd., Tokyo, Japan), 4.56 g ( 17.8 mmol) ΝΑΜΑ and 221.5 5 g PGME are equipped with magnetic stirring A 500 ml three-necked flask with a rod and a thermometer. A condenser with a nitrogen outlet adapter and a dropping funnel with a nitrogen inlet adapter were attached to the flask. The mixture was stirred at room temperature for about 4.5 minutes to produce a dusty state. Suspension / solution.

Next, a solution of 0.680 g (4.14 mmol) of AIBN in 73.60 g of PGME was prepared and charged into a dropping funnel. The reaction mixture was purged with nitrogen at room temperature for about 15 minutes, and then the flask was immersed in an oil bath at 106 ° C. When the reaction solution was stirred, the AIBN solution was added dropwise over 2 minutes. The reaction mixture was stirred at about 96 ° C to 104 ° C for 24 hours and then allowed to cool. Yield: 3 2 1.1 g solution (9 8 ◦ / 〇 recovery); 1 〇. i 9 wt 〇 / 〇 poly. The Mw of the nama-adamantyl polymer in the solution was determined by GPC to be 13,200 g/mol, and d was 2.34.

To precipitate the polymer from the solution, the aliquots of hexane were placed in a 4 liter beaker equipped with a cantilever stirrer and a stir bar. 1 〇〇 5 g of the polymer solution was charged into the dropping funnel, and then it was added dropwise to the lapser over 9 minutes.

Stir in hexane' and then stir for an additional 1 minute at room temperature. The solvent was removed by vacuum filtration. The beaker with the polymer was placed in a vacuum oven at 5% for 5 hours' and then dried at room temperature for 3*. The beaker was then placed in a vacuum oven for 21, 5 hours. The polymer was then ground into a powder using a mortar and pestle, followed by 50. (: Drying to constant weight in a vacuum oven. Yield: 6% (62% recovery). (iv) GPC measured the concentration of the polymer in the chamber as i3, J 43 201035690 g/mol, and D was 2.16. Example 20 Preparation of bottom anti-reflective coating by ruthenium-adamantyl polymer

The resulting bottom anti-reflective coating was spin coated onto a tantalum wafer at 1,50 rpm for 2:30 cores and then baked at 160 C for 60 seconds. The film and optical properties of the resulting ruthenium-containing adamantyl bottom anti-reflective coating and the properties of the bottom anti-reflective coating of the terpolymer containing less pAG prepared according to the procedure of Example 3 above are provided in Table 3 below. in. Next, 193 nm lithography was performed using an ASML ΠΟΟ-ArF scanner. The antireflective coating was spin coated onto the tantalum wafer at 1,500 rpm for 3 seconds, followed by baking at 16 (TC for 60 seconds. The resulting film had a thickness of about 4911111. Coating photoresist (ARX3001JN, with 190 Nm), and ρΑβ and PEB were performed at ii〇°c for 60 seconds. It was found that for dense L/s and isolated lines, PEB for 60 seconds at l〇6t would result in a less clean gap. Display illumination mode NA- target CD-developing - ring 0.75 0.85/0.567 130 nm 17260 nm P (bright field) ◦PD262 'duration 45 seconds 44 201035690 SEM cross section as shown in Figures 9(a) and 9(b) As shown in the photograph, for both dense and isolated lines', at a exposure dose of 25 mJ/cm2, a fine 130 nin L/S (1:1 and isolated line) was obtained at about 2.2 μπι DOF. Example 18- Film and optical results of 20 film thicknesses were only obtained from wafers used for EL stripping. For dark loss estimation, the coating was PEB at 10 10 for 60 seconds before the solvent was applied. Table 3. Bottom Anti-reflective coating film and optical properties bottom anti-reflective coating polymer adhesive film thickness EL peeling, % dark loss, % 19 3 nm n/k Example 3 Terpolymer I 52 nm +0.8 +0.6 1.66/0.54 Example 18 Terpolymer I 52.5 nm +0.8 +0.6 1.65/0.54 Example 20 Terpolymer I+NAMA 49 Nm -0.4 +0.8 1.67/0.50 Example 21 Terpolymer with less PAG j anti-reflective coating and additional 193 Q photoresist lithography comparison In this procedure, two commercially available photoresists are used and The bottom anti-reflective coating (IMp terpolymer I) containing less PAG prepared by the procedure in Example 3 above was subjected to the selected lithography. Each test was performed, i, then the bottom anti-reflective coating was spin-coated to On the Shixi wafer, it lasted for 1 second, and then baked for 60 seconds in the 16th generation. The film has a thickness of 55 nm. Then there will be a commercially available photoresist (TArF-; Pi6-001 from Ding OK, or from Shin_Etsu) SAIL_x i8i) is applied to the thin crucible. The conditions and exposure parameters for each photoresist are as follows: 45 201035690 TArF-Pi6-001 SAIL-X-181 PAB 110°C, lasts 60 seconds l〇5°C, duration 60 seconds anti-button agent thickness 130 nm 155 nm illumination mode custom dipole 35Y NA 0.75 0.75 σ 0.89 0.89:0.65 target CD 130 nm L/260 nm P (bright field) 80 mnL/160nmP (bright field) PEB 114°C for 60 seconds 110°C for 60 seconds Development OPD262 (45 seconds) OPD262 (45 seconds) Exposure using the ASML 1100-ArF scanner. The SEM cross section is shown in Figure 10. For the resist TArF-Pi6-001 (a), the lithographic results with resolution were shown at 0.0 / xm focal length. For resist SAIL-X-181 (b), at 1:1 and 1:1.5 L/S, at a focal length of 0·0 μηη and +0.1 μιη, the resolution is 130 nm. This anti-agent showed a lower photoacid diffusion/activity. In summary, this example demonstrates that the lower PAG-containing terpolymer I bottom anti-reflective coating of the present invention exhibits surprising compatibility with a variety of resists. Example 22 Sublimation of Terpolymer I Antireflective Coating Containing Less PAG In this procedure, the sublimation of the antireflective coating containing less PAG prepared according to the procedure of Example 3 during the baking step was Two commercially available sublimate materials of a 93 nm dry bottom anti-reflective coating were compared. A quartz crystal microbalance (QCM) was mounted over the nozzle attached to the glass bell jar. A vacuum is applied to raise the sublimate to the crystal for collection, wherein the condensed sublimate is recorded based on the change in crystal frequency. Do not measure the solvent that does not condense. Then connect 46 201035690 to the electrode of the crystal to transfer the data to the computer. "The real-time frequency curve of the computer green system" is calculated as the sublimation of the sublimate object. The hot time (in seconds) of the Nike number mark | 193 nm dry development The bottom anti-reflective coating control group was ARC® 29A-8 A ARC® 162-304-2 ( , 3⁄4 ^ | Brewer Science, Rolla'MO). For a terpolymer containing less PAG, a bottom anti-reflective coating (thickness 49.5 nm) with a baking parameter of 16 (rc for 12 sec seconds and for a dry bottom anti-reflective coating (thickness 75.3 nm, respectively) And 39·1 nm), the baking parameter is 2〇5t:, lasting 12 〇 seconds. The hot plate is maintained at the specified temperature for about 1 minute', then the newly coated wafer is placed under the glass bell jar for use. The results are summarized in Figure HU. The sublimation of the terpolymer with less PAG ϊ bottom anti-reflective coating is much less than the dry bottom anti-reflective coating ARC®29A-8, and the dry bottom The amount of sublimation of the anti-reflective coating ARC® 162-304-2 was approximately the same. Example 23 Comparison of Residues After Development on a Wafer Wafer In this procedure, a ternary copolymer containing less pAG prepared according to Example 3 was used. The amount of development I residue on the shi shi anti-reflective coating is compared to the residue of a commercially available wet-developable anti-reflective coating. The use of photoresist (ARX3001JN) and less PAG Terpolymer j bottom anti-reflective coating and arc® DS-A520 (from Brewer Science) The wafer is covered and processed using the ACT8Tel coating development system and the ASML PAS5S00TM/1100 scanner for exposure. The film thickness of both anti-reflective coatings is the same (55 nm) e at 1〇fC The bottom anti-reflective coating with less PAG is PEB for 6 sec seconds, while for 47 201035690 ARC®DS-A520, 1 l (PEB for TC lasts 60 seconds. The thickness of the photoresist film is 190 nm). Between 200 nm and at 11 〇. pAB was performed for 60 seconds. Using a conventional illumination, a tortuous dose matrix was generated using open frame exposure. After 45 seconds of development with OPD262, Woollam M2000 ellipsometry was used. The residual organic residue was measured. The results are shown in Figure 13 and show the post-development residue of the bottom anti-reflective coating with less PA G on the Shih-Chan substrate compared to the earlier generation aRC® DS-A520. The correlation between the thickness of the film and the film thickness is much lower. For the terpolymer I anti-reflective coating containing less PAG, a slight tendency to show the decrease of the residue as the film thickness increases is observed. Similar trends were observed in dose measurements. Topography on the substrate, The degree of change indicates that the residue of the bottom anti-reflective coating containing ruthenium-free PAG of the present invention should be smaller than that of the conventional wet-developable coating. The radiant energy variation in the range of 15 mj/cm2 to 61 mj/cm2 Causes the difference in residue after development of ARC®DS-A520. However, the ARX300 1JN and the bottom anti-reflective coating with less PAG have a minimal development after exposure range of 15 mJ/cm2 to 61 mJ/cm2. The residue changes. Example 24 Comparison of Post-Development Residues on a Tantalum Nitride Substrate In this procedure, two wet developable anti-reflective coatings were used to compare the amount of residue on a substrate deposited by tantalum nitride. A terpolymer containing 4 parent less PAGs prepared according to Example 3! The bottom anti-reflective coating and ARC® DS-A520 (from Brewer Science) were spin coated onto the same tantalum nitride substrate and then at i 6 〇. (3 bakes for 6 sec., for each composition, 48 201035690 to obtain a film thickness of 55 nm, then spin the photoresist (ARx3 〇〇 ijn) to 2 coated wafers under U (rc) After pAB 6 sec., a 190 nm resist film was produced. Open frame ArF radiation was performed using a Nik〇n NSR_S3 〇 7E tool, and then the PEB containing the lower bottom anti-reflective coating of the present invention was subjected to 1 〇 6 art. The ARC® DS-A520 was PEB for a period of 6 seconds at 114. The exposure stack was then developed for 60 seconds with nmd_3 (2.38% TMAH; Ohka America, MiIpiUs, ca). Figure 14 is a graph showing the residue data of the two kinds of bottom anti-reflective coatings in terms of the thickness of the residue relative to the exposure dose. The thickness of the nitride is measured at or near the measurement of each data point. The residue of the bottom anti-reflective coating of the diterpene copolymer I containing less PAG was significantly reduced with dose 2 to an asymptote of approximately 18 mJ/cm 2 , and then the amount of residue remained stable with the dose. Therefore, for 14 mJ/cm 2 Up to 25 mJ/cm2 of A&quot; typhoon agent, with traditional wet development resistance Compared to the shot coating, the bottom anti-reflective coating of the diterpene copolymer I containing less PAG is expected to produce less residue on the nitride substrate. It is also observed, especially at the scavenging dose (E〇), The bottom anti-reflective coating of the present invention containing less PAG produces the least residue. Example 25 Using a binary copolymer of a compared to y PAG, other lithography of the bottom anti-reflective coating In this procedure, the study uses light. Resistivity performance of an anthracite base anti-reflective coating containing less pAG prepared according to Example 3 under ARX3001JN (190 nm thickness). Exposure using an ASML n〇〇_ArF scanner, PAB at 1 UTC, PEB was carried out for 6 〇 seconds and at various coffee temperatures 49 201035690 110 ° c, 114 ° c ), each lasting 60 degrees (102 ° C, 106 t ' ll 〇 t seconds. The exposure conditions are shown below. Conventional 0.75 0.89 lighting mode NA- target CD-developing - 130 nm L/260 nm P (bright field) OPD262, lasts 45 seconds

The SEM cross-section photograph was prepared by identifying the optimum exposure dose at 25 mJ/cm2 SEM cross section and 〇.〇ιη focal length. A photograph of the resolution from 110 nm to 160 nm at PEB at 10 °C is shown in Figure i5(a). Acceptable L/S (1 · 1, 1:3, and isolated lines) at I% nm, 140 nm, 150 nm, and 160 nm resolution. At 120 nm resolution, dense (1:1) l/S is acceptable, but isolated lines are lost. The least residue was observed in the open area. At 130 nm resolution, the CD/SEM using KLA 8100XP caused an iso/dense bias of about 10 nm, which is within 1% of the target CD of i:3L/S and isolated lines. In all of the SEM photographs shown, at 120 nm to 160 nm resolution, the line exhibits undercut or pinch at its bottom. For i〇2°C and 106°CPEB, DOF is 〇_30 μηι, while ll〇°CPEB produces a slightly higher DOF of 0.40 μη. Since the undercut increases with increasing enthalpy, the U4°CPEB produces a 0.10 μηη DOF. Figure 15(b) contains the lithography results as a function of the PEB test. These data indicate that as the peb increases, the bottom anti-reflective coating undercut becomes more severe, indicating; j: the polyacid is diffused into the unexposed areas. This combination of anti-reflective coating and photoresist is considered to have a PEB window of approximately 50 201035690 8 °C. As shown by the outline in Figures i5(a)-(b), this photoresist produces a consistent acid diffusion into the bottom anti-reflective coating. Example 26 Other lithography of a terpolymer anti-reflective coating containing a less PAG terpolymer. In this procedure, the study was prepared according to Example 3 using a photoresist ARX3 340 J (JSR Micro) at a thickness of 230 nm. The resolution of the bottom anti-reflective coating of the terpolymer I containing less pag. Exposure was performed using an ASML 1250-ArF scanner, pAB was performed at ll 〇 ° C, and pEB was performed at various PEB temperatures (106 〇, 110 t, 114 〇 and U8 (t) for 60 seconds each. The exposure conditions are shown below. Illumination Mode - Conventional NA-0.85 σ-0.5 Target CD-150 nm S/375 nm ρ (Dark Field of View) Development - OPD262 'The resulting SEM cross-section photograph taken over 45 seconds is shown in Figure 16. For all low enthalpy temperatures, the DOF of these patterns is about 0.25 for exposure doses of 21 mJ/cm2, 20 mJ/cm2 and 20 (respectively). For the highest enthalpy temperature, at an exposure dose of 20 mj/cm2, 〇-------------------- Window. The top of the resist line appears in the dent 'and the bottom of the line - some slight undercuts' There is much less resistance to ARX3G() UN. As shown in Fig. I5(b), even with the increase of PEB temperature, the undercut of the anti-reflective coating is more consistent than that of ^ 51 201035690 when using photoresist arx3〇〇ijn. In summary, the photoresist arx334〇j exhibits good compatibility with the bottom anti-reflective coating, providing an acid sufficient to decrosslink the film and remove its protective groups. At the same time, the undercut is kept in the unexposed area. Therefore, although the PEB window is similar to the photoresist arx3〇〇un, the bottom anti-reflective coating profile characteristics are improved. Example 27 Vinyl ether crosslinker formulation

In this order, by using 25.15 g of butanediol monovinyl ether (Aldrich,

Preparation of Examples 2 and 3 by St Louis, MO), 22.91 g of triethylamine (Aldrich, St L〇uis, mo) and 250 ml of tetrahydrofuran (THF; Aldrich, 1 (10) is) were added to a $(8) ml 2-neck flask. Internal vinyl ether crosslinker (benzenetricarboxylic acid gin[4-(vinyloxy)butyl] ester) used in '5, 6, 8, 1, 1 , 12, 14, 1 6 1 8 and 20. The flask was equipped with a stir bar, an addition funnel, a condensate and a nitrogen inlet and outlet. The flask was immersed in an ice water bath and the solution was stirred under a nitrogen stream. Next, 20.00 g of ι,3,5-benzenetricarbonyltrioxane (Aldrich, st L〇U1S, M〇) was dissolved in 52 2010 35690 50 ml THF in a 250 ml Erlenmeyer flask. The solution was transferred to M, transferred to an addition funnel on a 500 ml 2-necked flask and added dropwise to a stirred a-alcohol early vinyl ether/triethylamine/THF solution t for about 15 minutes, straight, and The main body is added. A white sinking is formed upon contact. The flask was then removed from the ice bath +, ^^ and the slurry was allowed to reach room temperature in the flask for about 16 hours. The glare will stop. The upper and lower will heat the pulp to reflux for 4 hours. The flask was removed from the heat and allowed to cool to room temperature. The slurry was then filtered using a suction filtration configuration and concentrated using a rotary evaporator to give a viscous yellow liquid.

This liquid was dissolved in 100 ml of diethyl ether (Aldrich, st L〇uis, M〇) and washed with 25 〇 1 part of 12,5% aqueous solution of apex (8 1 (1 coffee, 11 乂〇仏, MO) 2 The ether layer was extracted with a separatory funnel and then washed twice with 5 〇w portions of deionized water. The ether layer was allowed to settle and collected. The ether layer was dehydrated by mixing the ether layer with 5.0 g of activated basic alumina. The mixture was stirred for 1 hour and gravity filtered. Concentrated clear yellow liquid in a rotary evaporator gave a yellow viscous oil. The total yield was about 29.28 g (yield: 77%). Example 28 Other vinyl ether crosslinker Formulation

In this embodiment, the preparation of another crosslinker is described. The crosslinker can be prepared by adding 24 7 g of 2-(vinyloxy)ethanol, 27.44 g of triethylamine, and 300 ml of THF to a 53 2010 35690 2k bottle. The solution can be immersed in an ice water bath and stirred under a stream of nitrogen. y, 24·01 g l3,5·benzenetricarbonyltrichloro can be dissolved in 250 ml of 10 〇 ml of THF in a flask. This solution was then added dropwise to the 2-(Ethyloxy)ethanol/triethylamine/THF solution until the addition was completed. The material can then be allowed to reach room temperature and then heated to reflux for about 4 hours. The slurry can be allowed to cool to room temperature and then filtered using a suction filtration configuration. The solution was then concentrated using a rotary evaporator to give a viscous yellow liquid. Next, the liquid was dissolved in 100 liters and washed in 50 ml portions of TMAH aqueous solution twice. The acetazone layer can then be extracted and 50 ml ^ deionized water used for m times. The B (tetra) is then dehydrated by anhydrous magnesium. At the end of the table, the solvent can be removed under pressure. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram depicting a novel article formed by the present invention; and a structure formed by the method (not shown in Fig. 2(a) showing the bottom anti-embossing of the working example embodiment in the absence of photoresist Comparative Curve of Reflective Coating Figure 2(b) shows the contrast curve and line of the bottom anti-reflective coating of the working example of the working example in the absence of photoresist.

T is exposed and 110 is used. (: PEB 2, 5, 8 '14 and 16 prepared drawings; Τ Exposure and use 120. (:: ΡΕΒ, 5, 8, 14 and 16 prepared drawings; Figure 2 (c) below shows coverage The photoresist is present for Example 2 T exposure of the working example and uses 110. (: PEB, 5, §, U, and ΐό prepared for each of the 54 201035690 bottom anti-reflective coatings; Figure 3 is from Example 2: Micromirror (SEM) cross-sectional photographs using various bottom anti-reflective coatings; &gt;, 8 and 14 of 193 nm lithography with 193 nm lithography of the exposure time shown The lower '38 nm bottom anti-reverse 54 nm-55 nm bottom anti-reflection 4 trace from the SEM cross-section photograph in Example 3: a) shot coating 'and b' at various exposure times, at various exposure times, Shot coating

Figure 5 shows SEM cross-sectional photographs from 2193 nm lithography using the bottom anti-reflective coating prepared in Example 6 at various exposure times; Figure 6 depicts the use of a bottom anti-reflective coating prepared in Example 1 using various exposure times. SEM cross-sectional photograph of the i 93 nm lithography performed by the layer; Figure 7 shows no SEM cross-sectional photograph of the i 93 nm lithography using the bottom anti-reflective coating prepared in Example π at various exposure times; Figure 8(4) I will be from a SEM cross-sectional photograph of dense and isolated lines of 193 nm lithography using the bottom anti-reflective coating prepared in Example i 8 at various exposure times; Figure 8(b) characterization of Figure 8(a) Magnified view of the best SEM cross-face of dense and isolated lines; Figure 9(a) does not come from the dense and isolated 193 ηιη lithography using the bottom anti-reflective coating prepared in Example 20 at various exposure times SEM cross-face photo of the line; Figure 9(b) is an enlarged view of the best SEM cross-section of the dense and isolated lines of Figure 9(a); 55 201035690

Figure 1 shows the bottom anti-reflective coating prepared using Example 21 and two different commercially available photoresists: a) TarF-Pi6-001 (from ΤΟΚ); and b) SAIL-X-181 (from Shin- Etsu) SEM cross-section photograph of 193 nm lithography; Figure 11 is a plot of the bottom anti-reflective coating prepared in Comparative Example 22 and two commercially available 1 93 nm dry bottom anti-reflective coatings over time. Figure 12 is a histogram of the total sublimate collected for each anti-reflective coating in Example 22; Figure 13 shows a comparison of the bottom anti-reflective coating of the present invention from Example 23 at different exposure doses. A graph of the post-development residue on the tantalum wafer and the residue of a commercially available wet developable anti-reflective coating; FIG. 14 is a comparison of the bottom anti-reflective coating of the present invention from Example 24 on the tantalum A graph of the residue after development and the residue of a commercially available wet developable anti-reflective coating; Figure 15 (a) shows tf from Example 25 in pEB at 1〇6〇c for 110 nm to 160 nm Analysis; f eve! _ SEM cross-section photograph of dense, semi-dense and isolated lines of 193 nm lithography; Figure 15(b) shows from the real b 1 shell in her case 25 at different PEB temperatures; j of 1 93 nm 4 Photograph of the SEM cross-section of the political image, and Figure 16 shows the use of the anti-reflective coating composition sheet from the example of the %. SEM cross-section of 193 nm lithography 56 201035690 [Main component symbol description]

Claims (1)

201035690 VII. Patent application scope: A method for forming a microelectronic structure, the method comprising: (a) providing a substrate having a surface; VIII) forming an anti-reflection layer on the surface of the β-ray, the anti-reflection layer being coated or The antireflective composition of the polymer dispersed in the solvent system comprises: a recycled monomer unit having an adamantyl group; and) a photoresist is applied to the antireflective layer to form an image forming layer. 2. The method of claim 1, wherein the adamantyl group is acid labile. A method of claim 1, wherein the antireflective composition further comprises a vinyl ether crosslinker. 4. The method of claim 1, wherein the method further comprises crosslinking the antireflective layer after the forming (b). The method of claim 4, wherein the crosslinking produces an antireflective layer that is substantially insoluble in the photoresist. The method of claim 4, wherein the adamantyl group does not participate in the crosslinking. 7. The method of claim 4, the method further comprising: (d) 4"" imaging layer, the anti-reflective layer is exposed to 帛# to produce the imaged layer and the exposed portion of the anti-reflective layer . 8. The method of claim 7, wherein the method further comprises: () contacting the imaging layer and the anti-reflective layer with a developer to remove the exposed portions from the surface of the substrate. The method of claim 7, wherein the exposure causes the anti-58 201035690 reflective layer to be decrosslinked. Ιο· 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 11. The method of claim 7, wherein the antireflection layer has an initial solubility in an inspective developer, and the exposure is + beta month horn, wherein the exposure of the antireflection layer after the exposure (d) Partly has a final solubility in the alkali hydrazine developer, the final solubility being greater than the initial solubility. 12. The method of claim 7, wherein the antireflective composition is substantially free of an acid generator, and wherein the imaging layer is produced during the exposure (d) The exposed portions of the antireflective layer de-crosslink the acid. The method of claim 1, wherein the polymer is selected from the group consisting of a first compound selected from the group consisting of adamantyl acrylate and carbitol acetonate. The second compound of the group consisting of the ethylene sulfonium compound, the acrylic compound, the methacrylic acid hydrazine compound, the hexamethyl quinone compound, the vinyl ether, the derivative thereof, and the combination thereof is formed by polymerization. 〇 14. A microelectronic structure comprising: a substrate having a surface; a cured anti-reflective layer adjacent to a surface of the substrate, the anti-reflective layer being anti-reflective comprising a polymer dissolved or dispersed in the system A composition is formed, the polymer comprising a cyclic monomer unit having an adamantyl group; and a photoresist layer adjacent to the antireflection layer. - 15. The structure of claim 14, wherein the antireflective composition further comprises a vinyl ether crosslinker. 59 201035690 16. The structure of the anti-reflective composition of claim 14 is substantially free of an acid generator. 17. The antireflection layer can be wet developed as in the structure of claim 16 of the patent application. 18. The adamantyl group is acid labile as claimed in claim 14. 19. According to the structure of claim 14, the substrate is selected from the group consisting of 石's SiGe, (10), ·, aluminum tungsten, tungsten telluride, gallium arsenide, germanium, antimony, tantalum nitride. , coral, black diamond, phosphorus-doped or boron-doped glass implant layer, titanium nitride, cerium oxide, cerium oxynitride, and mixtures of the foregoing. An anti-reflective composition comprising dissolved or dispersed in a solvent system, a t-crosslinked polymer, and a crosslinking agent, the polymer comprising a monomer unit having an adamantane and a cyclic group having an acid group Body unit. 21 Such as the composition of claim 20, the adamantyl group has acid instability. 2. The composition of claim 20, wherein the sulfonate ring monomer units having an acid group are selected from the group consisting of: Wherein: each Ri is selected from the group consisting of -Η, branched and unbranched alkyl, and cyclic group 60 201035690; and each R 2 is individually selected from Λ T ^-OH -L-OH'-C〇〇 A group consisting of H'L-COOH and -l_c(cf3)2oh, and f with medium L may be any suitable linking group. 23. The composition of the invention, wherein the cyclic monomer unit having a diamond base is selected from the group consisting of: / R1 '(II) ❹ OR3 wherein: each R1 is selected from the group consisting of -Η; and each R3 is individually selected as a branched and unbranched alkyl group, and a cyclic group. and Each of the R4 groups is individually selected from the group consisting of branched and unbranched alkyl groups and sulfhydryl groups. • The composition of claim 20 of the patent scope, wherein the polymer package has 3 ring-ring monomers: 61 201035690 Wherein: the branched and unbranched alkyl groups, and each of the cyclic groups R1 are selected from the group consisting of: and each R2 is individually selected from the white mountain, wherein L can be any suitable linking group 9 from -〇H, -L-OH, a group consisting of -COOH, -L-COOH and -lc(cf3)2〇h, group; and the following group: Each R3 line is individually selected from R4 Each of the R4 groups is individually selected from the group consisting of branched and unbranched alkyl groups and cyanomorphic groups. 25. The composition of claim 2, wherein the composition further comprises a dye. 26. The composition of claim 25, wherein the dye is bonded to the alpha polymer. 27. The composition of claim 20, wherein the cross-linking agent is 62